Transition metal complexes as dye forming catalysts in hair coloring compositions

ABSTRACT

A hair coloring composition comprising a first composition which comprises:  
     (a) a dye forming transition metal salt or complex; which is first applied to the hair;  
     and a second composition which comprises the following two compositions which are mixed just prior to application to the hair:  
     (a) a composition comprising a water-soluble peroxygen oxidizing agent; and  
     (b) a composition comprising one or more oxidative hair coloring agents selected from the group consisting of an aromatic diamine, an aminophenol, a polyhydric phenol a catechol and mixtures thereof.

BACKGROUND OF THE INVENTION

[0001] The difficulties in the development of hair coloringcompositions, which can deliver precise long-lasting colors with lowhair damage, are in part due to the inherent structure of the hairitself and in part due to the necessary harsh conditions of effectivehair coloration processes.

[0002] In general, the condition and structure of human hair is notregular along the length of the hair shaft. Human hair is subject tovarious chemical and mechanical treatments such as combing, brushing,shampooing, heating, perming as well as exposure to the sun. As such,the hair at the ends of the hair shaft will generally exhibit signs ofdamage relative to the new growth close to the scalp. This damage canlead to inconsistent coloration when the hair is dyed due to irregularuptake of the hair-coloring agents along the length of the hair shaft.Thus there is a need for hair coloring compositions which can deliversubstantially consistent hair color results throughout the hair.

[0003] Once the hair has been colored there is a desire for the color tobe resistant to the fading action of the sun and other exterior factorsand that the color is retained in a consistent manner for a predictableperiod of time. Thus it would be desirable to develop a hair coloringcomposition which exhibited reduced fade and provided improvedresistance to wash out during regular cleansing regimen. An additionaldifficulty commonly associated with the dyeing of human hair is the needfor dye systems that avoid any adverse effect on the hair and skin ofthe user.

[0004] To color human or animal hair using conventional oxidative dyetechnology it is generally necessary to treat the hair with a mixture ofsuitable oxidative coloring agents and at least one oxidizing agent andswelling agent at alkaline pHs. Hydrogen peroxide is the most commonlyused oxidizing agent. This can lead to undesirable hair damage. Theseundesirable effects are in part due to the necessary conditions ofconventional peroxide treatment, as part of the hair coloring process,which requires high pH (>pH 9), use of swelling agents such as ammonia,extended exposure (from 30 to 60 minutes) and relatively highconcentration of oxidizing solutions (up to 30% volume of oxygen) inorder to deliver effective hair dyeing and hair melanin bleaching. Thusthere is a need for hair coloring compositions, which can oxidize dyeprecursors and color the hair effectively without damage.

[0005] Oxidative dyes and peroxide oxidizing agents can be used todeliver a variety of hair colors to the hair. However such conventionalhair coloring compositions comprising oxidative dyes and peroxideoxidizing agent do not deliver against the key consumer needs of colorsaturation, color vividness, precise initial color predictability,improved wash fastness, improved safety and low hair damage.

[0006] Applicants have now found that the combination of peroxideoxidizing agents with certain transition metal salts or complexes andone or more oxidative coloring agents in hair coloring compositions candeliver excellent initial hair color in a faster time, good washfastness of the hair color over time, desirable color saturation andvividness attributes, and significantly reduced hair damage.Furthermore, applicants have found that the combination of these dyeprecursors and transition metal salts or complexes with a source ofperoxide at particular levels and ratios in the coloring compositions ofthe present invention can deliver these excellent hair coloringattributes results with minimal hair damage in a faster time.

[0007] Thus it is an object of the present invention to provide improvedhair coloring compositions.

[0008] The following publications relate to the field of the invention:

[0009] U.S. Pat. No. 6,004,355 discloses hair coloring compositionswhich comprise (a) a water-soluble peroxygen oxidizing agent, (b) anorganic peroxyacid precursor oxidizing aid, and (c) one or moreoxidative hair coloring agents. The compositions may be used inprocesses for coloring human or animal hair and may be convenientlyprovided in kits wherein each of the aforementioned components areindividually packaged. This patent, at column 23, lines 20-35, disclosesas a ligand, a list which includes1,4,7-trimethyl-1,4,7-triazacyclononane.

[0010] WO 97/24108, WO 97/24107 and U.S. Pat. No. 6,004,355 disclose ahair bleaching composition comprising: a) a water-soluble peroxygenbleach and (b) a bleaching aid selected from organic peroxyacid bleachprecursors and/or preformed organic peroxyacids. The products canprovide hair bleaching and in-use efficacy benefits including reducedhair damage at lower pH.

[0011] U.S. Pat. No. 5,873,910 discloses a process for the two-stageoxidation dyeing of keratin fibers by applying to the keratin fibers:

[0012] in a first stage, at least one composition A containing at leastone manganese salt and/or a manganese complex,

[0013] in a second stage, at least one composition B having a pH ofgreater than or equal to 6, and resulting from the extemporaneous mixingof at least one composition B1 containing at least one 4- substituted1-naphthol and at least one composition B2 containing at least oneoxidizing agent, and corresponding multi-compartment dyeing kit.

[0014] This patent discloses 1,4,7-trimethyl-1,4,7-triazacyclononane asa manganese complex to be used in its process at column 10, lines 20-25.

[0015] DE 19852972 discloses the use of1,4,7-trimethyl-1,4,7-triazacyclononane in hair dye formation.

SUMMARY OF THE INVENTION

[0016] The present invention is related to a hair coloring compositionsuitable for the treatment of human or animal hair. According to oneaspect of the present invention, there is provided a hair coloringcomposition comprising a first composition which comprises:

[0017] (a) a dye forming transition metal complex; which is firstapplied to the hair;

[0018] and a second composition which comprises the following twocompositions which are mixed just prior to application to the hair:

[0019] (a) a water-soluble peroxygen oxidizing agent; and

[0020] (b) one or more oxidative hair coloring agents selected from thegroup consisting of an aromatic diamine, an amino phenol, a polyhydricphenol, a catechol and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

[0021] As used herein, % means weight % of the total composition unlessotherwise designated. The compositions of the invention are made usingknown ingredients or with ingredients analogous to those known in theart. The packages or containers to be used with the compositions of theinvention are made using known processes and materials or by processesand materials which are analogous to those known in the art.

[0022] Compositions of the invention are used in a two step process forthe coloring and bleaching of hair. That is, the first recitedcomposition comprising dye forming transition metal catalysts iscontacted with the hair, and then the second composition is made bymixing the following two ingredients just prior to application to thehair; (a) a water-soluble peroxygen oxidizing agent; and (b) one or moreoxidative hair coloring agents. After mixture, this composition is thenapplied to hair. The coloring reaction takes place and the hair isrinsed.

[0023] As used herein the term “hair” to be treated may be “living” i.e.on a living body or may be “non-living” i.e. in a wig, hairpiece orother aggregation of non-living fibres. Mammalian, preferably human hairis preferred. However wool, fur and other melanin containing fibres aresuitable substrates for the compositions according to the presentinvention.

[0024] The hair coloring compositions can contain, in addition to amixture of active oxidizing agents, transition metal salts or complexesand oxidative coloring agents such as, by way of example, sequestrants,thickeners, buffers, carriers, surfactants, solvents, antioxidants,polymers non-oxidative dyes and conditioners.

[0025] As noted above, there is provided a hair coloring compositioncomprising a first composition which comprises:

[0026] (a) a dye forming transition metal complex or salt;

[0027] which is first applied to the hair; and a second composition,which comprises the following two compositions which are mixed justprior to application to the hair:

[0028] (a) a water-soluble peroxygen oxidizing agent; and

[0029] (b) one or more oxidative hair coloring agents selected from thegroup consisting of an aromatic diamine, an amino phenol, a polyhydricphenol, a catechol and mixtures thereof.

[0030] The invention also relates to a composition comprising atransition metal wherein the transition metal salt and/or transitionmetal complex is selected from group 1B, 6B, 7B or 8B metals and anazamacrocycle;

[0031] a composition wherein a water-soluble peroxygen oxidizing agentis selected from hydrogen peroxide, sodium perborate, sodiumpercarbonate, and urea peroxide complexes;

[0032] a composition wherein the transition metal complex is formed froma manganese salt and 1,4,7-trimethyl-1,4,7-triazacyclononane;

[0033] a composition wherein said manganese complex isbis(octahydro-1,4,7-trimethyl-1H-1,4,7-triazinone-N1, N4,N7)-tri-mμ-oxodimanganese bis hexafluorophosphate;

[0034] a composition wherein the weight ratio of water-soluble peroxygenoxidizing agent to transition metal complex is in the range of fromabout 6000:1 to about 1:2;

[0035] a composition wherein the weight ratio of water-soluble peroxygenoxidizing agent to transition metal complex is from about 2000:1 toabout 1:1;

[0036] a composition wherein the weight ratio of water-soluble peroxygenoxidizing agent to transition metal complex is from about from 600:1 toabout 60:1;

[0037] a composition wherein the said transition metal salt and/ortransition metal catalyst are present in a concentration ranging from0.0001% to 0.2% by weight of metal equivalents relative to the totalweight of composition;

[0038] a composition wherein the said transition metal salt and/ortransition metal catalyst are present in a concentration ranging from0.001% to 0.1% by weight of metal equivalents relative to the weight ofthe total composition;

[0039] a composition which further comprises a buffering agent;

[0040] a composition having one or more oxidative hair coloring agentsas described above which has a pH of about 5 to about 11;

[0041] a composition as described above which further comprises asurfactant selected from the group consisting of anionic, nonionic,cationic, zwitterionic, amphoteric surfactants and mixtures thereof; and

[0042] a hair coloring kit comprising an individually packaged oxidizingcomponent with additional agents, an individually packaged componenthaving one or more hair coloring agents and an individually packagedtransition metal salt and/or transition metal complex with additionalagents which when mixed forms a composition of the invention.

[0043] According to a further aspect of the present invention, there isprovided a hair coloring composition comprising:

[0044] (b) from about 0.0001% to about 2% by weight of a transitionmetal and a second composition which comprises the following twocompositions, which are mixed just prior to application to the hair:

[0045] (a) a composition comprising from about 0.01% to about 10% byweight of a water-soluble peroxygen oxidizing agent;

[0046] (b) a composition comprising from about 0.0001% to about 7% byweight of one or more oxidative hair coloring agents;

[0047] The invention also relates to compositions for coloring human oranimal hair wherein the hair coloring composition comprises:

[0048] (a) a composition comprising from about 0.001% to about 1.0% byweight of a transition metal salt and/or transition metal complex;

[0049] which is first applied to the hair; and a second composition,which comprises the following two compositions which are mixed justprior to application to the hair:

[0050] (a) a composition comprising from about 0.5% to about 20% byweight of a water-soluble peroxygen bleaching compound

[0051] (b) a composition comprising from about 5% to 50% additionalagents selected from surfactants, buffering agents, oxidation basesand/or couplers from about 20% to about 95.5% by weight of an inertdiluent

[0052] The invention also relates to a process for coloring human oranimal hair wherein the hair coloring composition comprises applying tothe hair the compositions described above.

[0053] It has been found that compositions of the present invention areunexpectedly effective for lightening and coloring very dark brown orblack hair.

[0054] For example, when (a) a dye forming transition metal complexcomposition of the present invention is first applied to very dark brownhair or black hair;

[0055] and then a second composition which comprises (a) a water-solubleperoxygen oxidizing agent; and (b) a composition comprising one or moreoxidative hair coloring agents the following two compositions (which aremixed just prior to application to the hair) are applied to said verydark hair brown or black hair there is obtained a very dramatic changecolor of the hair.

[0056] Change in hair color can be measured by means which are known inthe art. A customary scale for measuring the change in hair color isdefined in terms of the variables: L, a, and b wherein L, a, and b aredefined as follows: L indicates the lightness or darkness of the colorvalue. The higher the L, therefore, the lighter the hair, and the morefading that has occurred. When L is 0, the hair is black, and when L is100, the hair is white. −a and +a represent changes in color tone fromgreen to red. −b and +b represent the changes in color tone from blue toyellow.

[0057] What follows now is a description of the ingredients which may beused in the compositions of the invention.

[0058] Dye Forming Transition Metal Complex or Salt

[0059] The compositions of the invention comprise a transition metalcontaining catalyst for the peroxide oxidizing agents. One suitable typeof catalyst is a catalyst system comprising a heavy metal cation ofdefined catalytic activity, such as copper or manganese cations, anauxiliary metal cation having little or no catalytic activity, such aszinc or aluminum cations, and a sequestrant having defined stabilityconstants for the catalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 which is herebyincorporated by reference.

[0060] Other types of suitable catalysts include the manganese-basedcomplexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No.5,244,594 which is hereby incorporated by reference.

[0061] Preferred examples of these catalysts include Mn^(IV)₂(μ-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, Mn^(III)2(μ-O)1 (μ-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(ClO₄)2, Mn^(IV)₄(μ-O)₆(1,4,7-triazacyclononane) 4-(ClO₄)2, Mn^(III)Mn^(IV)₄(μ-O)₁(μ-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane) 2-(ClO₄)3, andmixtures thereof. Others are described in EP-A-0,549,272 which is herebyincorporated by reference. Other ligands suitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane,1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

[0062] For examples of suitable catalysts see U.S. Pat. No. 4,246,612and U.S. Pat. No. 5,227,084 which is hereby incorporated by reference.See also U.S. Pat. No. 5,194,416 which is hereby incorporated byreference which teaches mononuclear manganese (IV) complexes such asMn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃-(PF6). Still anothertype of suitable catalyst, is disclosed in U.S. Pat. No. 5,114,606,which is hereby incorporated by reference. It is a water-soluble complexof manganese (III) and/or (IV) with a ligand which is a noncarboxylatepolyhydroxy compound having at least three consecutive C—OH groups.Other examples include binuclear Mn complexed with tetra-N-dentate andbi-N-dentate ligands, including N₄Mn^(III)(μ-O )₂Mn^(IV)N₄)+ and[Bipy2Mn^(III)(μ-O)₂Mn^(IV)bipy2]-(ClO₄)₃.

[0063] Further suitable catalysts are described, for example, inEP-A0,408,131 (cobalt complex catalysts), EP-A-0,384,503, andEP-A-0,306,089 which is hereby incorporated by reference(metallo-porphyrin catalysts), and U.S. Pat. No. 4,728,455 all of whichare hereby incorporated by reference.

[0064] Also suitable is (manganese multidentate ligand catalyst), U.S.Pat. No. 4,711,748 and EP-A 0,224,952, (absorbed manganese onaluminosilicate catalyst), U.S. Pat. No. 4,601,845; (aluminosilicatesupport with manganese and zinc or magnesium salt), U.S. Pat. No.4,626,373 (manganese ligand catalyst), U.S. Pat. No. 4,119,557 (cobaltchelant catalyst) CA-A-866,191 (transition metal containing salts), U.S.Pat. No. 4,430,243 (chelants with manganese cations and noncatalyticmetal cations); and U.S. Pat. No. 4,728,455 (manganese gluconatecatalysts); all of which are hereby incorporated by reference.

[0065] Other types of suitable catalysts include the manganese-basedsalts as described in U.S. Pat. No. 5,873,610 which is herebyincorporated by reference.

[0066] The compositions of the invention comprise one or more transitionmetal catalysts. When compared against a combination of all of thecompositions of the invention after they have been mixed together (thatis, the dye forming transition metal complex; the water-solubleperoxygen oxidizing agent composition; and the composition containingone or more oxidative hair coloring agents selected from the group) theconcentration of each catalyst is from about 0.0001% to about 1% byweight and is preferably from about 0.001% to about 0.1% by weight.

[0067] The total combined level of catalysts in the compositionsaccording to the present invention is from about 0.0001% to about 2%,preferably from about 0.001% to about 0.2%, more preferably from about0.001% to about 0.1% by weight.

[0068] Water-Soluble Peroxygen Oxidizing Agents

[0069] The compositions of the invention may comprise at least onewater-soluble peroxygen oxidizing agent. Water-soluble as defined hereinmeans a peroxygen oxidizing agent compound, which can be substantiallysolubilized in water.

[0070] The peroxygen oxidizing agents useful herein are generallyinorganic peroxygen materials capable of yielding hydrogen peroxide inan aqueous solution. Water-soluble peroxygen oxidizing compounds arewell known in the art and include hydrogen peroxide, inorganic alkalimetal peroxides such as sodium periodate and sodium peroxide and organicperoxides such as urea peroxide, melamine peroxide, and inorganicperhydrate salt oxidizing compounds, such as the alkali metal salts ofperborates, percarbonates, perphosphates, persilicates, persulphates andthe like. These inorganic perhydrate salts may be incorporated asmonohydrates, tetrahydrates, and the like. Mixtures of two or more suchoxidizing agents can be used if desired. Preferred for use in thecompositions according to the present invention is hydrogen peroxide.

[0071] When compared against a combination of all of the compositions ofthe invention after they have been mixed together (that is, the dyeforming transition metal complex; the water-soluble peroxygen oxidizingagent composition; and the composition containing one or more oxidativehair coloring agents), the peroxygen oxidizing agent is present in thecompositions of the present invention at a level of from about 0.01% toabout 9%, preferably from about 0.1% to about 6%, more preferably fromabout 0.2% to about 4% by weight.

[0072] Oxidative Hair Coloring Agents

[0073] The compositions of the present invention may include one or moreoxidative hair coloring agents. Such oxidative hair coloring agents areused in combination with the oxidizing systems of the present inventionto formulate permanent, hair dye compositions.

[0074] Permanent hair dye compositions as described herein arecompositions, which once applied to the hair are substantially resistantto wash-out. Wash-out as described herein is the process by which haircolor is removed from the hair over time during normal hair cleansingregimen.

[0075] When compared against a combination of all of the compositions ofthe invention after they have been mixed together (that is, the dyeforming transition metal complex; the water-soluble peroxygen oxidizingagent composition; and the composition containing one or more oxidativehair coloring agents), the concentration of each oxidative hair coloringagent is from about 0.0001% to about 7% by weight and is preferably fromabout 0.001% to about 2.0% by weight.

[0076] When compared against a combination of all of the compositions ofthe invention after they have been mixed together (that is, the dyeforming transition metal complex; the water-soluble peroxygen oxidizingagent composition; and the composition containing one or more oxidativehair coloring agents), the total combined level of oxidative haircoloring agents in the compositions according to the present inventionis from about 0.01% to about 15%, preferably from about 0.01% to about10%, more preferably from about 0.1% to about 5% by weight.

[0077] Oxidative hair coloring agents which can be used in compositionsof the invention can be selected from the group consisting of anaromatic diamine, an aminophenol, a polyhydric phenol, a catechol andmixtures thereof. Oxidative hair coloring agents which can also becalled oxidative dyes are described in more detail below.

[0078] The dye forming intermediates used in oxidative dyes can bearomatic diamines, aminophenols and their derivatives. These dye-formingintermediates can be classified as; primary and secondary intermediates.Primary intermediates are chemical compounds, which by themselves willform a dye upon oxidation. The secondary intermediates, are also knownas color modifiers or couplers and are used with other intermediates forspecific color effects or to stabilize the color.

[0079] The oxidation dye intermediates which are suitable for use in thecompositions and processes herein include aromatic diamines, polyhydricphenols, aminophenols and derivatives of these aromatic compounds (e.g.,N-substituted derivatives of the amines, and ethers of the phenols).Primary oxidation dye intermediates are generally colorless moleculesprior to oxidation. The oxidation dye color is generated when theprimary intermediate is activated and subsequently joined with asecondary intermediate (coupling agent), which is also generallycolorless, to form a colored, conjugated molecule.

[0080] In general terms, oxidation hair dye precursors or intermediatesinclude those monomeric materials which, on oxidation, form oligomers orpolymers having extended conjugated systems of electrons in theirmolecular structure. Because of the new electronic structure, theresultant oligomers and polymers exhibit a shift in their electronicspectra to the visible range and appear colored. For example, oxidationdye precursors capable of forming colored polymers include materialssuch as aniline, which has a single functional group and which, onoxidation, forms a series of conjugated imines and quinoid dimers,trimers, and the like, ranging in color from green to black. Compoundssuch as p-phenylenediamine, which has two functional groups, are capableof oxidative polymerization to yield higher molecular weight coloredmaterials having extended conjugated electron systems. Color modifiers(couplers), such as those detailed hereinafter, are preferably used inconjunction with the oxidation dye precursors herein. A representativelist of oxidation dye precursors suitable for use is found in Sagarin,“Cosmetic Science and Technology Interscience, Special Edn. Vol 2 pages308 to 310, which is hereby incorporated by reference.

[0081] The typical aromatic diamines, polyhydric phenols, aminophenols,and derivatives thereof, described above as primary dye precursors canalso have additional substituents on the aromatic ring, e.g. halogen,aldehyde, carboxylic acid, nitro, sulfonic acid and substituted andunsubstituted hydrocarbon groups, as well as additional substituents onthe amino nitrogen and on the phenolic oxygen, e.g. substituted andunsubstituted alkyl and aryl groups.

[0082] Nonlimiting examples of suitable aromatic diamines, aminophenols,polyhydric phenols and derivatives thereof, respectively, are thefollowing compounds:

[0083] o-phenylenediamine,

[0084] m-phenylenediamine,

[0085] 2-nitro-p-phenylenediamine,

[0086] 1,3,5-triaminobenzene,

[0087] 2-hydroxy-p-phenylenediamine,

[0088] 2,4-diaminobenzoic acid,

[0089] sodium 2,4-diaminobenzoate,

[0090] calcium di-(2,4-aminobenzoate),

[0091] ammonium 2,4-diaminobenzoate,

[0092] trimethylammonium 2,4-diaminobenzoate,

[0093] tri-(2-hydroxyethyl)ammonium 2,4-diaminobenzoate,

[0094] 2,4-diaminobenzaldehyde carbonate,

[0095] 2,4-diaminobenzenesulfonic acid,

[0096] potassium 2,4-diaminobenzenesulfonate,

[0097] N,N-diisopropyl-p-phenylenediamine bicarbonate,

[0098] N,N-dimethyl-p-phenylenediamine,

[0099] N-ethyl-N′-(2-propenyl)-p-phenylenediamine,

[0100] N-phenyl-p-phenylenediamine,

[0101] N-phenyl-N-benzyl-p-phenylenediamine,

[0102] N-ethyl-N′-(3-ethylphenyl)-p-phenylenediamine,

[0103] 2,4-toluenediamine,

[0104] 2-ethyl-p-phenylenediamine,

[0105] 2-(2-bromoethyl)-p-phenylenediamine,

[0106] 2-phenyl-p-phenylenediamine laurate,

[0107] 4-(2,5-diaminophenyl)benzaldehyde,

[0108] 2-benzyl-p-phenylenediamine acetate,

[0109] 2-(4-nitrobenzyl)-p-phenylenediamine,

[0110] 2-(4-methylphenyl)-p-phenylenediamine,

[0111] 2-(2,5-diaminophenyl)-5-methylbenzoic acid,

[0112] 2-methoxy-p-phenylenediamine,

[0113] 2,3-dimethyl-p-phenylenediamine,

[0114] 2,5-dimethyl-p-phenylenediamine,

[0115] 2-methyl-5-methoxy-p-phenylenediamine,

[0116] 2,6-methyl-5-methoxy-p-phenylenediamine,

[0117] 3-methyl-4-amino-N,N-diethylaniline,

[0118] N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,

[0119] 3-methyl-4-amino-N,N-bis-(2-hydroxyethyl)aniline,

[0120] 3-chloro-4-amino-N,N-bis-(2-hydroxyethyl)aniline,

[0121] 4-amino-N-ethyl-(piperidonoethyl)aniline,

[0122] 3-methyl-4-amino-N-ethyl-p-(piperidonoethyl)aniline,

[0123] 4-amino-N-ethyl-N-(morpholinoethyl)aniline,

[0124] 4-amino-N-ethyl-N-(acetylaminoethyl)aniline,

[0125] 4-amino-N-(methoxyethyl)aniline,

[0126] 3-methyl-amino-N-ethyl-N-(2-acetylaminoethyl)aniline,

[0127] 4-amino-N-ethyl-N-(mesylaminoethyl)aniline,

[0128] 3-methyl-4-amino-N-ethyl-N-(β-mesylaminoethyl)aniline,

[0129] 4-amino-N-ethyl-N-(β-sulfoethyl)aniline,

[0130] 3-methyl-4-amino-N-ethyl-N-(β-sulfoethyl)aniline,

[0131] N-(4-aminophenyl)morpholine,

[0132] N-(4-aminophenyl)piperidine,

[0133] 2,3-dimethyl-p-phenylenediamine,

[0134] 2-isopropyl-p-phenylenediamine,

[0135] N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulfate,

[0136] o-aminophenol,

[0137] m-aminophenol,

[0138] p-aminophenol,

[0139] 2-iodo-p-aminophenol,

[0140] 2-nitro-p-aminophenol,

[0141] 3,4-dihydroxyaniline,

[0142] 3,4-diaminophenol,

[0143] 2-hydroxy-4-aminobenzoic acid,

[0144] 2-hydroxy-4-aminobenzaldehyde,

[0145] 3-amino-4-hydroxybenzenesulfonic acid,

[0146] N,N-diisopropyl-p-aminophenol,

[0147] N-methyl-N-(1-propenyl)-aminophenol,

[0148] N-phenyl-N-benzyl-p-aminophenol sulfate,

[0149] N-methyl-N-(3-ethylphenyl)-p-aminophenol,

[0150] 2-nitro-5 -ethyl-p-aminophenol,

[0151] 2-nitro-5-(2-bromoethyl)-p-aminophenol,

[0152] (2-hydroxy-5-aminophenyl)acetaldehyde,

[0153] 2-methyl-p-aminophenol,

[0154] (2-hydroxy-5-aminophenyl)acetic acid,

[0155] 3-(2-hydroxy-5-aminophenyl-1-propene,

[0156] 3-(2-hydroxy-5-aminophenyl)-2-chloro-1-propene,

[0157] 2-phenyl-p-aminophenol palmitate,

[0158] 2-(4-nitrophenyl)-p-aminophenol,

[0159] 2-benzyl-p-aminophenol,

[0160] 2-(4-chlorobenzyl-p-aminophenol perchlorate,

[0161] 2-(4-methylphenyl)-p-aminophenol,

[0162] 2-(2-amino-4-methylphenyl)-p-aminophenol,

[0163] p-methoxyaniline,

[0164] di-(2-aminoethyl-4-aminophenyl) ether,

[0165] di-(2-hydroxyethyl-4-aminophenyl) ether,

[0166] (4-aminophenoxy)acetaldehyde,

[0167] (4-aminophenoxy)acetic acid,

[0168] (4-aminophenoxy)methanesulfonic acid,

[0169] 1-propenyl-4-aminophenyl ether isobutyrate,

[0170] di-(2-chloro-1-propenyl-4-aminophenyl) ether,

[0171] di-(2-nitro-1-propenyl-4-aminophenyl) ether,

[0172] di-(2-amino-propenyl-4-aminophenyl) ether,

[0173] di-(2-hydroxy-1-propenyl-4-aminophenyl) ether,

[0174] N-methyl-p-aminophenol,

[0175] 3-methyl-4-aminophenol,

[0176] 2-chloro-4-aminophenol,

[0177] 3-chloro-4-aminophenol,

[0178] 2,6-dimethyl-4-aminophenol,

[0179] 3,5-dimethyl-4-aminophenol,

[0180] 2,3-dimethyl-4-aminophenol,

[0181] 2,5-dimethyl-4-aminophenol,

[0182] 2-hydroxymethyl-4-aminophenol,

[0183] 3-hydroxymethyl-4-aminophenol,

[0184] o-hydroxyphenol (catechol),

[0185] m-hydroxyphenol (resorcinol),

[0186] p-hydroxyphenol (hydroquinone),

[0187] 4-methoxyphenol,

[0188] 2-methoxyphenol,

[0189] 4-(2-chloroethoxy)phenol,

[0190] 4-(2-propenoxy)phenol,

[0191] 4-(3-chloro-2-propenoxy)phenol,

[0192] 2-chloro-4-hydroxyphenol (2-chlorohydroquinone),

[0193] 2-nitro-hydroxyphenol (2-nitrohydroquinone),

[0194] 2-amino-4-hydroxyphenol,

[0195] 1,2,3-trihydroxybenzene (pyrogallol),

[0196] 2,4-dihydroxybenzaldehyde,

[0197] 3,4-dihydoxybenzoic acid,

[0198] 2,4-dihydroxybenzenesulfonic acid,

[0199] 3-ethyl-4-hydroxyphenol,

[0200] 3-(2-nitroethyl)-4-hydroxyphenol,

[0201] 3-(2-propenyl)-4-hydroxyphenol,

[0202] 3-(3-chloro-2-propenyl)-4-hydroxyphenol,

[0203] 2-phenyl-4-hydroxyphenol,

[0204] 2-(4-chlorophenyl)-4-hydroxyphenol,

[0205] 2-benzyl-4-hydroxyphenol,

[0206] 2-(2-nitrophenyl)-4-hydroxyphenol,

[0207] 2-(2-methylphenyl)-4-hydroxyphenol,

[0208] 2-(2-methyl-4-chlorophenyl)-4-hydroxyphenol,

[0209] 2-methoxy-4-(1-propenyl)phenol,

[0210] 4-hydroxy-3 methoxycinnamic acid,

[0211] 2,5-dimethoxyaniline,

[0212] 2-methylresorcinol,

[0213] aniline,

[0214] p-chloroaniline,

[0215] p-fluoroaniline,

[0216] p-nitroaniline,

[0217] p-aminobenzaldehyde,

[0218] p-aminobenzoic acid,

[0219] sodium p-aminobenzoate,

[0220] lithium p-aminobenzoate,

[0221] calcium di-(p-aminobenzoate),

[0222] ammonium p-aminobenzoate,

[0223] p-aminobenzenesulfonic acid,

[0224] potassium p-aminobenzenesulfonate,

[0225] N-methylaniline,

[0226] N-propyl-N-phenylaniline,

[0227] N-methyl-N-2-propenylaniline,

[0228] N-benzylaniline,

[0229] N-(2-ethylphenyl)aniline,

[0230] 4-methylaniline,

[0231] 4-(2-bromoethyl)aniline,

[0232] 2-(2-nitroethyl)aniline,

[0233] 4-aminophenylacetaldehyde,

[0234] 4-aminophenylacetic acid,

[0235] 4-(2-propenyl)aniline acetate,

[0236] 4-(3-bromo-2-propenyl)aniline,

[0237] 4-phenylaniline chloroacetate,

[0238] 4-(3-chlorophenyl)aniline,

[0239] 4-benzylaniline,

[0240] 4-(4-iodobenzyl)aniline,

[0241] 4-(3-ethylphenyl)aniline,

[0242] 4-(2-chloro-ethylphenyl)aniline,

[0243] phenol,

[0244] p-chlorophenol,

[0245] p-nitrophenol,

[0246] p-hydroxybenzaldehyde,

[0247] p-hydroxybenzoic acid,

[0248] p-hydroxybenzenesulfonic acid,

[0249] ethylphenyl ether,

[0250] di-(2-chloroethylphenyl) ether,

[0251] di-(2-nitroethylphenyl) ether,

[0252] phenoxyacetaldehyde,

[0253] phenoxyacetic acid,

[0254] 3-phenoxy-1-propene,

[0255] 3-phenoxy-2-nitro-1-propene,

[0256] 3-phenoxy-2-bromo-1-propene,

[0257] 4-propyiphenol,

[0258] 4-(3-bromopropyl)phenol,

[0259] 2-(2-nitroethyl)phenol,

[0260] 4-hydroxyphenylacetaldehyde,

[0261] 4-hydroxyphenylacetic acid,

[0262] 4-(2-propenyl)phenol,

[0263] 4-phenyiphenol

[0264] 4-benzylphenol,

[0265] 4-(3-fluoro-2-propenyl)phenol,

[0266] 4-(4-chlorobenzyl)phenol,

[0267] 4-(3-ethylphenyl)phenol

[0268] 4-(2-chloro-3-ethylphenyl)phenol,

[0269] 2,5-xylenol,

[0270] 2,5-diaminopyridine,

[0271] 2-hydroxy-5-aminopyridine,

[0272] 2-amino-3-hydroxypyridine,

[0273] tetraaminopyrimidine,

[0274] 1,2,4-trihydroxybenzene

[0275] 1,2,4-trihydroxy-5-(C₁-C₆-alkyl)benzene,

[0276] 1,2,3-trihydroxybenzene,

[0277] 4-aminoresorcinol,

[0278] 1,2-dihydroxybenzene,

[0279] 2-amino-1,4-dihydroxybenzene,

[0280] 2-amino-4-methoxyphenol,

[0281] 2,4-diaminophenol,

[0282] 3-methoxy-1,2-dihydroxybenzene,

[0283] 4,6-dimethoxy-3-amino-1-hydroxybenzene,

[0284] 2,6-dimethyl-4-(p-hydroxyphenyl)amino]phenol

[0285] and salts thereof.

[0286] Additional oxidation dye couplers suitable for use herein includecatechol species and in particular catechol “dopa” species whichincludes dopa itself as well as homologs, analogs and derivatives ofDOPA. Other suitable dye precursors are dihydroxyindole (DHI),dihydroxyindolecarboxylic acid (DHICA) and derivatives thereof,indolines and derivatives thereof. Examples of suitable catechol speciesinclude cysteinyl dopa, alpha alkyl dopa having 1 to 4, preferably 1 to2 carbon atoms in the alkyl group, epinephrine and dopa alkyl estershaving 1 to 6, preferably 1 to 2 carbon atoms in the alkyl group.

[0287] The oxidation dye couplers (precursors) can be used herein aloneor in combination with other oxidation dye couplers (precursors)mentioned above. The choice of a single dye coupler (precursor) will bedetermined by the color, shade and intensity of coloration which isdesired. The following are preferred oxidation dye couplers (precursors)which can be used herein, singly or in combination, to provide oxidationhair dyes having a variety of shades ranging from ash blonde to black;these are: pyrogallol, resorcinol, p-toluenediamine, o-phenylenediamine,m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol,nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine, m-aminophenol,2-amino-3-hydroxypyridine, N,N bis (2-hydroxyethyl)p-phenylenediamine,4-amino-2-hydroxytoluene, 1,5-dihydroxynapthalene 2,4-diaminoanisole,hydroquinone, 4-amino-2-hydroxytoluene, 2-methyl resorcinol,2-methyl-5-hydroxyaminophenol, 6-amino-3-hydroxy-toluene,2,5-diaminotoluene, and 1-phenyl-3-methyl-pyazolone. These can be usedin the molecular form or in the form of peroxide-compatible salts, asdetailed above.

[0288] Applicant has also found that compositions of the presentinvention comprising particular oxidizing agents with particulartransition metal salts or catalysts with oxidative dyes are valuable forthe delivery of good high intensity colors with reduced levels of dyeand peroxide. In particular applicant has now found that good haircoloring results can be achieved using the oxidizing systems of thepresent invention and up to about 84% less dye versus conventional haircoloring compositions. As such the compositions according to the presentinvention are valuable for the delivery of good initial color and washfastness over time in addition to having low hair damage attributes.

[0289] Solvents

[0290] Water is the preferred principal diluent for the compositionsaccording to the present invention. As such, the compositions of presentinvention may also include one or more solvents as additional diluentmaterials. Generally, the solvent is selected to be miscible with waterand innocuous to the skin. Solvents suitable for use herein includeC₁-C₂₀mono- or polyhydric alcohols and their ethers, glycerine, withmonohydric and dihydric alcohols and their ethers preferred. In thesecompounds, alcoholic residues containing 2 to 10 carbon atoms arepreferred. Thus, a particularly preferred group includes ethanol,isopropanol, n-propanol, butanol, propylene glycol, ethylene glycolmonoethyl ether, and mixtures thereof.

[0291] The compositions of the invention may also include the followingmaterials.

[0292] Buffering Agents

[0293] The coloring compositions of the present invention may have a pHin the range of from about 5 to about 11, more preferably from about 6to about 8, and especially from about 6 to about 7.

[0294] As herein before described the preferred coloring compositions ofthe present invention may contain one or more buffering agents and/orhair swelling agents (HSAs) to adjust the pH to the desired level.Several different pH modifiers can be used to adjust the pH of the finalcomposition or any constituent part thereof.

[0295] Thickeners

[0296] The composition containing one or more oxidative hair coloringagents of the present invention (coloring compositions) may additionallyinclude a thickener at a level of from about 0.05% to about 20%,preferably from about 0.1% to about 10%, more preferably from about 0.5%to about 5% by weight. Thickening agents suitable for use in thecompositions of the invention may be selected from the group consistingof oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearylalcohol, stearyl alcohol, and synthetic thickeners; and mixturesthereof.

[0297] Surfactant Materials

[0298] The compositions of the present invention may additionallycontain a surfactant system. Suitable surfactants for inclusion in thecompositions of the invention generally have a lipophilic chain lengthof from about 8 to about 22 carbon atoms and can be selected from thegroup consisting of anionic, cationic, nonionic, amphoteric,zwitterionic surfactants and mixtures thereof.

[0299] Materials used in compositions of the invention may be employedin the following ranges:

[0300] Hair Coloring Composition Example 1 (which shows ranges ofingredients) Ingredients % w/w Oxidative dyes 0.01-15 Sequestrant0.01-1  Antioxidant 0.01-3  Solvent  2.0-35 Buffering agent 0.01-10Thickener 0.05-20 Surfactants  5.0-40 Water to 100

[0301] Ranges of ingredients which can be included in Hair ColoringCompositions of the invention Example 2 (which shows ranges ofingredients) Ingredients % w/w p-Phenylenediamine Oxidative dyes0.0001-7  4-Amino-2-Hydroxytoluene Oxidative dyes 0.0001-7 p-Aminophenol Oxidative dyes 0.0001-7  2-Methylresorcinol Oxidative dyes0.0001-7  Phenyl-methyl-pyrazolone Oxidative dyes 0.0001-7 N,N-bis-2-hydroxyethyl-PPD sulfate Oxidative dyes 0.0001-7 3-Methyl-4-aminophenol Oxidative dyes 0.0001-7  Sodium sulphiteAntioxidant 0.01-3 Sodium EDTA Sequestrant 0.01-1 Sodium isoascorbateAntioxidant 0.01-3 Propylene glycol Solvent  2.0-35 Oleic acid (5 Titre)Buffering agent  0.01-10 Isopropanol Solvent  2.0-35 Perfume oilFragrance  0.1-1 Dihydroxyethyl soyamine dioleate Surfactants  5.0-40PEG3 Cocamine Surfactants  5.0-40 Water balance

[0302] As used here in PPD means p-phenylene-diamine.

[0303] Ranges of ingredients which can be included in CatalystCompositions of the invention 1,4,7-trimethyl-1,4,7-triazacyclononanetri-μ-oxo- 0.0001-1 manganese complex Water To balance

[0304] Example 3 (which shows ranges of ingredients) DeveloperFormulation or composition containing water-soluble peroxygen oxidizingagent Chemical Name % (w/w) Sequestrant 0.01-1  Antioxidant 0.01-3 Solvent  2.0-35 Buffering agent 0.01-10 Thickener 0.05-20 Surfactants 5.0-40 Oxidizing agent 0.01-9  Water to balance 100

EXAMPLE 4 (Which Shows Ranges of Ingredients)

[0305] Chemical Name % (w/w) Catalyst Formulation (or transition metalsalt or complex formulation) Catalyst 0.0001-1   Solvent q.s. Developerformulation Oxidizing agent 0.01-9 Water to balance to 100

[0306] The following is example 5 is a specific example of a compositionof the invention that was made.

EXAMPLE 5

[0307] Ingredients Wt % p-Phenylenediamine 0.05 4-Amino-2-hydroxytoluene0.0172 p-Aminophenol 0.2 2-Methylresorcinol 0.3 Phenyl-methyl-pyrazolone0.02 N,N-bis-2-hydroxyethyl-PPD sulphate 0.001 3-methyl-4-aminophenol0.006 Sodium sulphite 1 Sodium isoascorbate 0.15 propylene glycol 8.6Oleic acid 8.6 Isopropanol 12.5 Perfume oil 0.5 Dihydroxyethyl soyaminedioleate 22.2 PEG3 cocamine 8 Water q.s

EXAMPLE 6

[0308] Developer Formulation which includes the water- soluble peroxygenoxidizing agent Chemical Name % (w/w) Ceteareth-7 1 Polyquaternium 37 150% Hydrogen peroxide 12 85% Phosphoric acid 0.03 Water to balance 100

[0309] Dye forming transition metal complex which is a ManganeseCatalyst Formulation Chemical Name % (w/w) Surfactant 11,4,7-trimethyl-1,4,7-triazacyclononane 0.1 tri-μ-oxo-manganese complexWater to balance 100

[0310] Preparation of dye composition—that is, the composition whichcomprises oxidative hair coloring agents:

[0311] Buffering agent, surfactants, perfume oil and solvent are mixedat 55° C. to obtain a homogenous solution (part 1). Deionized water isadded to the beaker and mixing is continued. Antioxidants are addedfollowed by solvent and nitrogen blanketing is begun. Dyes are added andthe mixture is heated to 50-55° C. and further mixed until the solutionis clear. The solution is cooled to 40-45° C. and more water is added.

[0312] Preparation of dye forming transition metal complex:

[0313] Add deionized water to beaker and begin mixing. Add surfactants,and thickener followed by catalyst and remaining ingredients to water.

[0314] Preparation of water-soluble peroxygen oxidizing agentformulation which is also known as developer formulation:

[0315] Add deionized water to beaker and begin mixing. Add surfactants,thickener and buffering agents follow by oxidizing agent and remainingingredients to water.

[0316] How to use Compositions of the Invention

[0317] As described above, a first composition of the inventioncomprises:

[0318] (a) a dye forming transition metal salt or complex.

[0319] As described above a second composition of the inventioncomprises a mixture of the following two compositions:

[0320] (a) a water-soluble peroxygen oxidizing agent; and

[0321] (b) one or more oxidative hair coloring agents selected from thegroup consisting of an aromatic diamine, an amino phenol, a polyhydricphenol, a catechol and mixtures thereof.

[0322] The hair to be colored can first be made wet with water. Then adye forming transition metal salt or complex as described above, can beapplied to the hair. Application temperatures may be in the range from15 to 40 degrees C. Then a water-soluble peroxygen oxidizing agent; andone or more oxidative hair coloring agents as described above, arethoroughly mixed together, and soon after, this mixture is applied tothe hair . Again application temperatures may be in the range from 15 to40 degrees C. After a contact time of about 5 to about 30 minutes, thehair is thoroughly rinsed.

[0323] While the invention has been described in connection withpreferred embodiments, this description is not intended to limit theinvention to the particular embodiments set forth. To the contrary, thisdescription is intended to cover such alternatives, modifications, andequivalents as may be included within the spirit and scope of theinvention as defined by the appended claims.

What is claimed is:
 1. A composition for coloring hair which comprises afirst composition comprising: (a) a dye forming transition metal salt orcomplex; and a second composition which comprises the following twocompositions which are mixed just prior to application to the hair: (a)a composition comprising a water-soluble peroxygen oxidizing agent; and(b) a composition comprising one or more oxidative hair coloring agentsselected from the group consisting of an aromatic diamine, anaminophenol, a polyhydric phenol a catechol and mixtures thereof.
 2. Acomposition according to claim 1, wherein said oxidative hair coloringagent is a transition metal salt and/or transition metal complexselected from group 1B, 6B, and 7B metals and an azamacrocycle.
 3. Acomposition according to claim 1, wherein the water-soluble peroxygenoxidizing agent is selected from the group consisting of hydrogenperoxide, sodium perborate, sodium percarbonate, and urea peroxidecomplexes.
 4. A composition according to claim 2, wherein the transitionmetal complex is formed from a manganese salt and1,4,7-trimethyl-1,4,7-triazacyclononane.
 5. A composition according toclaim 4, wherein said manganese complex isbis(octahydro-1,4,7-trimethyl-1H-1,4,7-triazinone-N1, N4,N7)-tri-mμ-oxodimanganese bis hexafluorophosphate.
 6. A compositionaccording to claim 2, wherein the weight ratio of the water-solubleperoxygen oxidizing agent to the transition metal salt and/or complex isin the range of from about 6000:1 to about 1:2.
 7. A compositionaccording to 6, wherein the weight ratio of the water-soluble peroxygenoxidizing agent to the transition metal salt and/or complex is fromabout 2000:1 to about 1:1.
 8. A composition according to claim 7,wherein the weight ratio of the water-soluble peroxygen oxidizing agentto the transition metal complex is from about 600:1 to about 60:1.
 9. Acomposition according to claim 2, wherein the transition metal saltand/or transition metal catalyst are present in a concentration rangingfrom about 0.0001% to about 0.2% by weight of metal equivalents relativeto the total weight of composition.
 10. A composition according to claim2, wherein the transition metal salt and/or transition metal catalystare present in a concentration ranging from about 0.001% to about 0.1%by weight of metal equivalents relative to the weight of the totalcomposition
 11. A composition according to claim 1, which comprises oneor m ore oxidative hair coloring agents which further comprises abuffering agent.
 12. A composition according to claim 11, which has a pHof about 5 to about
 11. 13. A composition according to claim 1, whichfurther comprises a surfactant selected from the group consisting ofanionic, nonionic, cationic, zwitterionic, amphoteric surfactants andmixtures thereof.
 14. A process for coloring human or animal hair whichcomprises applying to said hair a composition comprising: (a) from about0.001% to about 1.0% by weight of a transition metal salt and/ortransition metal complex; and then applying to said hair a secondcomposition which comprises the following two compositions which aremixed just prior to said second application to the hair: (a) acomposition comprising from about 0.5% to about 20% by weight of awater-soluble peroxygen oxidizing agent; and (b) a compositioncomprising one or more oxidative hair coloring agents selected from thegroup consisting of an aromatic diamine, an aminophenol, a polyhydricphenol a catechol and mixtures thereof. wherein the compositioncomprising one or more oxidative hair coloring agents has a pH of fromabout 5 to about
 11. 15. A process for lightening and coloring very darkbrown or black hair which comprises applying to said hair a compositioncomprising (a) from about 0.001% to about 1.0% by weight of a transitionmetal salt and/or transition metal complex; and then applying to saidhair a second composition which comprises the following two compositionswhich are mixed just prior to said second application to the hair: (a) acomposition comprising from about 0.5% to about 20% by weight of awater-soluble peroxygen oxidizing agent; and (b) a compositioncomprising one or more oxidative hair coloring agents selected from thegroup consisting of an aromatic diamine, an aminophenol, a polyhydricphenol a catechol and mixtures thereof. wherein the compositioncomprising one or more oxidative hair coloring agents has a pH of fromabout 5 to about
 11. 16. A hair coloring kit comprising an individuallypackaged oxidizing component, an individually packaged component havingone or more hair coloring agents, and an individually packagedtransition metal salt and/or transition metal complex component whereinsaid components are compositions are in accordance with claim 1.